Hydroxy-cyanoalkyl naphthalenes



' growth on plant cuttings.

Patented June 10, 1947 Albert F. Hardman, Akron,

Wlngfoot Corporation,

ration of Delaware Ohio, alsilnor to Akron, Ohio, at corpo- No Drawing. Application October 24, 1945,

GCIahns- (or. 260-405) This invention relates to a grou of valuable organic chemicals useful as intermediates in the fatty acids which have utility in promoting root More particularly, the invention relates to a series 01. nitriles which can preparation or hydroxy naphthalene substituted be converted to acids, amides and esters by procedures known to and described by the prior art. It is well known that certain organic acids and their derivatives are useful as stimulants for plant growth-and especially in stimulating root growth.

on plant cuttings. Generally, these acids are complex and diflicult-to synthesize. Accordingly, it is the purpose of this invention to provide inexpensive intermediates which are readily derived from cheap and commercially available raw ma-. terials. A further purpose is to provide methods of preparing the said intermediates.

The new compounds are the l-(2-cyanoalkyl) 2- hydroxy naphthalenes and are prepared by the reaction of 2-naphthol, otherwise known as beta naphthol, with acrylonitrile or an alpha-alkylsubstituted acrylonitrile, such as methacrylonitrile and ethacrylonitrile. in the, presence of substantial quantities of alkali metal hydroxide. The reaction is preferably conducted in a solution or suspension of the reactants in an inert solvent, such as benzene, toluene, petroleum ether or other hydrocarbon. The reactants are heated to a temperature between 50 C. and 150 C., which may be the reflux temperature of the reaction mixture, in a flask provided with a water cooled condenser. Benzene is preferably used as the inert liquid and the temperature maintained between 75" C. and 85 C. When the reaction is completed the mass is mixed with an equal volume of water and the non-aqueous liquid separated. It is well known that phenol, and other compounds having hydroxyl groups substituted on aromatic rings, will react with acrylonitrile in the presence of sodium metal catalyst to form mixed ethers in accordance with the following equation:

(Na) OOH 0112:0110:

oo-cmcmorr The present reaction is quite unusual in that the hydroxyl radical remains unchanged and the substitution takes place on the alpha carbon atom z adJacent to the carbon to which the hydroxyl group is attached. This reaction proceeds as follows:

GHr-CHr-CN Example A benzene solution (55 cc.) containing 29 grams of Z-naphthol and 12 grams of acrylonitrile was mixed with 9 grams of sodium hydroxide pellets and heated on a steam bath in a reaction vessel provided with a water-cooled reflux condenser. The mixture was refluxed for two hours. cc. of cold water were added and the two-phase liquid was stirred until all 01 the sodium hydroxide was dissolved. The two liquid phases were then separated and the aqueous solution filtered and treated with acetic acid. 3'7 grams of 2-hydroxy-l-naphthalenepropionitrile were precipitated. After recrystallization from an ethyl alcohol solution, a white solid having a melting point of 142 C. was secured. It had the following structure:

CHr-CHr-CN By the employment of an alpha-alkyl substituted acrylonitrile in place of the acrylonitrile in Example 1, other compounds of similar structure can be prepared, for example 1-(2-cyano-npropyl) -2-hydroxy-naphthalene and 1-(2-cyanon-butyi) .-2-hydroxy-naphthalene. These new nitriles may be converted to acids byrefluxing in the presence of sodium hydroxide followed by treatment with a strong mineral acid. The acids 3' aopreperedmoybeconvertedtolsetoneshyhectinsatreiiuxtemperctureinotoluenelolution. The isetone may then be converted tom umide by relction with gaseous ammonia. Other mes iortheneweomponndswillbereedilyoppermt to a, skilled chemist. Q

This npplicntion is e. continustion-in-pcrt of application Serial No. 556,490, filed September 29, 1944.

Although the inventionhssbeen describedwith respecttoaapeciiicex ample, itisnotintended that the detsils'thereoi should be construed as limitations upon the scope or the invention exoepttotheextentincorporstedinthctoliowinz claims.

I claim:

1. A 1-(2-cyanoalkyl) -2-h7dronnaphthnlene.

2. 1-(2-cyanoethyD2-hydroxy nsphthslen 3. l-(fl-cyano-n-propyDfl-hydron naphtha- 4. A method oi preparing 1-(2-cynno'nlk1D-2- z-naphthol and a, compound of the map cansistin oi'ocrylonitrileondelphlclkylsubctituted ecrylonitriles in the presence of on alkcli metal 5. A method of mepnrin: 1-(2-cyonoethyD2- presence of an alkali metal hydroride.

ALBERT F. EAR-DEAN.

REFERENCES CITED The following references are of record in the the of this patent:

FOREIGN PATENTS Number Coun Date 670,357 Germany Jan. 1'7, 1939 833,734 mace Oct. 28, 1988 

